U.S. patent number 6,830,326 [Application Number 10/279,605] was granted by the patent office on 2004-12-14 for enhancement of ink jet image waterfastness with overprinting.
This patent grant is currently assigned to Hewlett-Packard Development Company, L.P.. Invention is credited to Howard A. Doumaux, Yi-Hua Tsao.
United States Patent |
6,830,326 |
Tsao , et al. |
December 14, 2004 |
**Please see images for:
( Certificate of Correction ) ** |
Enhancement of ink jet image waterfastness with overprinting
Abstract
In a four pen ink jet printer comprising cyan, yellow, magenta,
and black inks, a clear liquid is applied to printed ink on a print
medium via a fifth pen, thereby fixing the colorants, which in turn
improves the durability of the printed ink. The clear fixer fluid
comprises at least one organic acid and, optionally, a salt of at
least one polymeric acid.
Inventors: |
Tsao; Yi-Hua (San Diego,
CA), Doumaux; Howard A. (San Diego, CA) |
Assignee: |
Hewlett-Packard Development
Company, L.P. (Houston, TX)
|
Family
ID: |
24289031 |
Appl.
No.: |
10/279,605 |
Filed: |
October 23, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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572712 |
May 16, 2000 |
6503978 |
Jan 7, 2003 |
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Current U.S.
Class: |
347/98; 106/31.6;
427/411; 427/333; 427/407.1; 523/160; 524/609; 524/610;
524/556 |
Current CPC
Class: |
B41J
11/0015 (20130101); B41M 7/0018 (20130101) |
Current International
Class: |
B41M
7/00 (20060101); B41J 11/00 (20060101); B41M
5/00 (20060101); B41J 002/01 (); B05D 003/10 ();
B05D 001/36 (); C09D 011/02 (); C09D 005/00 (); C08L
033/02 (); C08L 081/00 (); C08L 085/02 () |
Field of
Search: |
;347/98,100
;427/333,407.1,411 ;524/556,609,610 ;523/160,161 ;106/31.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0587164 |
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Mar 1995 |
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EP |
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1009279 |
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Jan 1989 |
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JP |
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01063185 |
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Mar 1989 |
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JP |
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11349873 |
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Dec 1999 |
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JP |
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WO 99/64249 |
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Dec 1999 |
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WO |
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Primary Examiner: Shosho; Callie
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION(S)
The present application is a divisional application of application
Ser. No. 09/572,712, filed on May 14, 2000, now U.S. Pat. No.
6,503,978, issued on Jan. 7, 2003, incorporated herein by
reference. The present application is related to application Ser.
No. 09/572,714, also filed on May 16, 2000, now U.S. Pat. No.
6,412,935, issued on Jul. 2, 2002, incorporated herein by
reference. The present application is directed to the composition
of a fixer fluid used in over-printing, while the related
application is directed to the mechanics of over-printing the fixer
fluid.
Claims
What is claimed is:
1. A method of fixing a printed ink printed by an ink jet printer,
said printed ink comprising an ink composition that would
precipitate or flocculate at a pH of about 6 or less, said method
comprising: (a) printing at least one ink on a print medium, said
at least one ink "having a colorant consisting essentially of at
least one" pigment to form a pigment-based ink, said print medium
being selected from the group consisting of porous and semi-porous
having a coating thereon selected from the group consisting of
alumina and silica; and (b) overprinting said ink with a clear
fixer fluid comprising a fixing component consisting essentially of
at least one organic acid and, optionally, a salt of at least one
polymeric acid.
2. The method of claim 1 wherein said organic acid is selected from
the group consisting of mono-functional, di-functional, and
poly-functional organic acids.
3. The method of claim 2 wherein said organic acid is present in
said fixer fluid in a concentration within a range of about 1 to 15
wt %.
4. The method of claim 3 wherein said organic acid is present in
said fixer fluid in a concentration within a range of about 2 to 7
wt %.
5. The method of claim 2 wherein said organic acid is selected from
the group consisting of acetic, glycolic, malonic, malic, maleic,
ascorbic, succinic, glutaric, fumaric, citric, tartaric, lactic,
sulfonic, and ortho-phosphoric acid and derivatives thereof.
6. The method of claim 5 wherein said organic acid is selected from
the group consisting of succinic acid, citric acid, and glycolic
acid.
7. The method of claim 1 wherein said polymeric acid is selected
from the group consisting of polyvinyl phosphonic acid, polymers
with phosphate groups, polystyrene sulfonic acid, and polymers
containing sulfonate or carboxylate groups.
8. The method of claim 7 wherein said salt comprises a cation
associated with said polymeric acid and wherein said cation is
selected from the group consisting of sodium, ammonium, and
potassium.
9. The method of claim 1 wherein polymeric acid is present in said
fixer fluid in a concentration within a range of about 1 to 10 wt
%.
10. The method of claim 1 wherein said fixer has a pH within a
range of about 2to 5.
11. The method of claim 1 wherein said ink jet printer includes
four pens, each containing an ink, at least one of said inks
containing said pigment and a fifth pen containing said clear fixer
fluid.
12. The method of claim 11 wherein said overprinting is performed
by over-printing said at least one pigment-based ink with said
fixer fluid by advancing said print medium a few dot rows per print
swath and either (i) applying said fixer fluid to said at least one
pigment-based ink on an N.sup.th pass where said fixer fluid pen
trails said at least one ink-printing pen, or (ii) printing an
additional swath without an advance of said print medium with said
fixer fluid where said fixer fluid pen leads said at least one
ink-printing pen.
Description
TECHNICAL FIELD
The present invention is related generally to ink jet printing and,
more particularly, to improving the waterfastness of the printed
ink.
BACKGROUND ART
Ink jet color printers commonly have four separate color pens, or
cartridges: cyan, yellow, magenta, and black, for providing a full
gamut of colors and hues. Such ink jet color printers are commonly
called "four pen" printers.
Porous media has been shown to give instant dry time printing with
an ink jet printer. However, print quality, as evidenced by
waterfastness, for example, may be compromised by improving other
qualities, such as dry time.
With an increased demand for outdoor signage and window displays,
efforts have been made to increase the durability of ink jet print
by printing pH-sensitive pigmented inks on porous media provided
with a coating. The coating typically comprises a bottom coating of
silica and a top coating of alumina; see, e.g., U.S. patent
application Ser. No. 09/491,642, filed Jan. 27, 2000. Adjusting the
pH in the coating helps to immobilize the pH-sensitive pigmented
inks, resulting in better waterfastness. However, adjusting the pH
in the coating is sometimes not desirable, due to flocculation of
the inorganic filler used in the coating fluid at desired pH or
image quality (IQ) tradeoff due to flocculation of the pH-sensitive
pigmented ink. Also, for media which are not designed to work with
certain ink sets, durability is impossible to be achieved without
post processing, e.g., lamination.
Thus, there is a need for improved waterfastness on printed porous
media without the need for post processing.
DISCLOSURE OF INVENTION
In accordance with the present invention, a clear liquid is applied
to the print via a fifth pen, thereby fixing the colorants, which
in turn improves the durability of the printed ink. The clear fixer
fluid comprises at least one organic acid and, optionally, a salt
of at least one polymeric acid.
Also in accordance with the invention, a method is provided for
fixing a printed ink printed by an ink jet printer, the printed ink
comprising an ink composition that would precipitate or flocculate
at a pH of about 6 or less. The method comprises: (a) printing at
least one ink on a print medium, the ink(s) containing a pigment to
form a pigment-based ink; and (b) overprinting the ink with the
clear fixer fluid.
The clear fixer fluid enhances the wet rub durability,
smearfastness, and waterfastness of pigmented ink printed on porous
and/or semi-porous alumina- or silica-coated print media.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation depicting a conventional
two-pass print mode comprising printing a swath on a print medium
and advancing the print medium by one-half swath height and
printing the remainder of the top portion of the swath and the
first half of the lower swath;
FIG. 2 is a view similar to that of FIG. 1, but depicting a
modified print mode comprising printing a swath on a print medium
and advancing the print medium a few dot rows, printing the
remainder of the top portion of the swath and the first portion of
the lower swath, then advancing the print medium nearly a full
swath;
FIG. 3 is a view similar to that of FIG. 2, but depicting the
combination of the modified print mode with also overprinting a
fixer; and
FIG. 4 is a top plan view depicting a five pen carriage design,
combining four color pens and a fixer pen.
BEST MODES FOR CARRYING OUT THE INVENTION
The wet rub durability, smearfastness, and waterfastness of
pigmented inks printed on porous and/or semi-porous alumina- or
silica-coated media (also called porous or semi-porous media) may
be enhanced by lamination, which can be costly and prone to
operator error. A more desirable procedure would be to have the
printer apply the overcoat fixer fluid during the printing
process.
Dry-time is enhanced by using porous coatings containing alumina or
silica. Capillary force draws the fluid into the porous matrix and
fills the pores much faster than relying on polymer swelling in
other conventional, non-porous coatings. Depending on pore volumes
existing in the porous coating, sometimes underprinting is less
desirable because the fixer fluid may fill the pores, resulting in
ink flooding, or excess ink flowing on the surface of the print
medium, when ink is printed.
The alumina and silica-based coatings noted above are substantially
transparent and should not adversely impact the hue, chroma, or
optical density of the inks. The transparent nature of these
coatings differentiates them from "plain paper" media, where
penetration of the inks into these media substantially reduces
their chroma and optical density. By using an underprinted fixer
fluid, it is possible to raise the chroma and optical density of
pigmented inks on plain paper. However, it is expected to be
desirable to overprint the fixer fluid rather than underprinting
(or some combination of over- and underprinting) the fixer fluid
when silica- or alumina-coated media are used. Application of the
fixer fluid prior to or during ink application may also result in
undesirable area fill nonuniformity due to immediate flocculation
of the color pigment.
Silica- and alumina-coated media have been shown to require
multi-pass printing in order to deliver high image quality (IQ) and
reasonable throughput. In a multi-pass printmode, only the terminal
1/N.sub.pass nozzles of the fixer pen would operate the terminal
nozzles, where N.sub.pass is the number of passes in the printmode.
A substantial portion of the pen nozzles would not be utilized,
exerting undue load on the nozzles in use. In a printer primarily
devoted to plain paper printing, this type of print mode may be
acceptable, as a small portion of the printer's life would be spent
print on porous/semi-porous media. However, large-format or
specialty printers under consideration are generally designed to
print on porous/semi-porous media for the majority of their life.
Therefore, it is desirable to spread the duty cycle over the entire
printhead to enhance printhead life.
One way of doing this is to utilize a variant on a printmode
developed within Hewlett-Packard Company for eliminating hue shifts
caused by bi-directional printing on plain paper; see, e.g., U.S.
patent application Ser. No. 09/363,943, filed Jul. 29, 1999, now
U.S. Pat. No. 6,254,217. This printmode works by printing a first
printing a swath, and then advancing the paper a small number of
dot rows to help reduce banding due to mis-directed or missing
nozzles (for a two-pass printmode, the prior art practice is to
advance the paper one-half of the swath height, as shown in FIG.
1). The return swath then covers nearly the same portion of the
paper. This printmode thus forces the hue shift into a few dot rows
per swath.
A similar method may also be used to apply the fixer fluid
overcoat. The image is still printed in a series of swaths, but
instead of performing a N.sub.nozzles /N.sub.pass dot row advance,
the media is not advanced or is only advanced a few dot rows per
pass; N.sub.nozzles is the number of nozzles in use on the
printhead and N.sub.pass is the number of passes in the printmode.
On the Nth pass, the fixer fluid is applied if the fixer fluid pen
is trailing the printing pens. If the fixer fluid pen is leading on
this swath, an additional swath is printed without a media advance.
Only the fixer fluid pen prints on this pass. The media is then
advanced the fall swath height of the pen minus the cumulative
number of dot rows advanced in the printing process (see FIG. 2).
If an odd number of passes are used, this method may require an
additional swath per section of media printed. If two overcoat
fixer fluid pens are used, no additional swaths are required (it is
presumed that the fixer fluid pen(s) resides at the one (or both)
ends of the pen cartridge). An additional refinement of this
technique is to position the fixer fluid pen slightly behind the
other pens so that it can overprint the dots advanced out of the
normal print zone during the printing process and to prevent
migration of the fixer fluid into the region being printed (see
FIG. 3).
As shown in FIG. 4, the carriage 10 of a printer thus comprises
four pens 12, 14, 16, and 18, each containing one of the colors
cyan, yellow, magenta, and black. A fifth pen 20 contains the fixer
fluid. The motion of the carriage is bi-directional across the
paper, as indicated by arrow 22, while the print medium (e.g.,
paper) 24 advances along the paper, as indicated by arrow 26.
Although a bi-directional example is described above,
uni-directional printing is also an optional way of employing this
technique.
The fixer fluid contained in the fifth pen 20 comprises at least
one organic acid and, optionally, at least one salt of a polymeric
acid. Examples of organic acids that may be suitably employed in
the practice of the invention include, but are not limited to,
mono-, di-, and polyfunctional organic acids. In general, it is
contemplated that any water-soluble organic acid having a pKa equal
to or less than that of the pH-sensitive colorant of concern may be
suitably employed. Preferably, one of the following classes of
organic acids is employed: acetic, glycolic, malonic, malic,
maleic, ascorbic, succinic, glutaric, fumaric, citric, tartaric,
lactic, sulfonic, and ortho-phosphoric acid and derivatives
thereof. Examples of polymeric acids include polyacrylic acid,
polyvinyl phosphonic acid and other polymers with phosphate groups
(R--PO.sub.3 or R--O--PO.sub.3), polystyrene sulfonic acid, and
polymers containing sulfonate and carboxylate groups. The cation
associated with the polymeric acid may comprise sodium, ammonium,
or potassium. The polymeric acid salt acts as a buffer.
The fixer fluid has a pH in the range of about 2 to 5. A pH less
than about 2 is too corrosive for the ink jet print cartridge
components, while a pH greater about 5 adversely affects the
ability of the fixer to destabilize the pigment dispersion,
"fixing" the pigment to the page.
The total concentration of organic acid and polymeric acid salt is
within the range of about 1 to 15 wt % of the fixer fluid.
Preferably, succinic acid is employed as the organic acid, in a
concentration within the range of about 2 to 7 wt % of the fixer,
preferably at a pH of about 4, as adjusted with a base, such as
sodium hydroxide or .beta.-alanine. The sodium salt of poly-acrylic
acid (mw=2,000 or mw=20,000) having a concentration within the
range of about 1 to 10 wt % of the fixer may additionally be
employed in the practice of the present invention.
Other preferred organic acids include citric acid and glycolic
acid. Preferred polymeric acids include polyvinyl phosphonic acid
and polystyrene sulfonic acid.
The fluid fixer also includes co-solvents commonly employed in the
inks, such as 1,5-pentanediol, 2-pyrrolidone, and
2-ethyl-2-(hydroxymethyl)-1,3-propanediol. Other co-solvents may
also be used, along with additional components often found in ink
jet inks, such as surfactants, biocides, and the like, for
controlling printability and reliability in ink jet printing.
Other components commonly added to ink-jet inks, such as solvents,
penetrants, biocides, and the like, may also be added to the fixer
solution of the present invention for improving pen performance and
reliability. Such other components may include ammonium nitrate,
EHPD (2-ethyl-2-(hydroxymethyl)-1,3-propanediol), 1,5-pentanediol,
and/or 2-pyrrolidone.
EXAMPLES
Pens containing acid and the polymeric acid or salt form were
filled (Table I). Magenta solid fill area was printed on a porous
media on an H-P 2500CP printer. Similar to what is disclosed in
above-referenced application Ser. No. 09/491,642, the porous media
had a two-layer structure. The top layer (coated at 20 g/m.sup.2)
contained 89 wt % alumina boehmite and 11 wt % binder, such as
polyvinyl alcohol. The base layer (coated at 25 g/m.sup.2)
contained 78 wt % silica and 22 wt % binder, such as polyvinyl
alcohol.
The magenta pen was then taken out and replaced by the test pen.
The same print file was used to print the clear fixer fluid on the
magenta-printed sheet, except the sheet was fed backward. The print
file was designed such that part of the magenta ink-covered area
was overprinted with the clear fixer fluid.
TABLE I Formulations of the Clear Fixer Fluid. Ink Ingredient
Percent Grams A. Acidic Fixing Fluid 1,5-pentanediol 8 40.00
2-pyrrolidinone 7.5 37.50 EHPD 7.5 37.50 Dowfax 8390 1 5.00
Tergitol 15-S-5 0.5 7.50 ammonium nitrate 0.5 2.50 succinic acid 7
35.00 DI Water 335.00 Total 500.00 Adjust to pH 4 with beta-alanine
B. Acidic Fixer Fluid 1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5
37.50 EHPD 7.5 37.50 ammonium nitrate 0.5 2.50 succinic acid 7
35.00 DI Water 347.50 Total 500.00 Adjust to pH 4 with beta-alanine
C. Acidic Fixer Fluid 1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5
37.50 EHPD 7.5 37.50 ammonium nitrate 0.5 2.50 succinic acid 7
35.00 DI Water 347.50 Total 500.00 D. Acidic Fixer Fluid
1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5 37.50 EHPD 7.5 37.50
ammonium nitrate 0.5 2.50 glycolic acid 7 35.00 DI Water 347.50
Total 500.00 E. Acidic Fixer Fluid 1,5-pentanediol 8 40.00
2-pyrrolidinone 7.5 37.50 EHPD 7.5 37.50 ammonium nitrate 0.5 2.50
citric acid 7 35.00 DI Water 347.50 Total 500.00 F. Acidic Fixer
Fluid 1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5 37.50 EHPD 7.5
37.50 ammonium nitrate 0.5 2.50 succinic acid 7 35.00 Na PAA 2000 3
15.00 DI Water 347.50 Total 515.00 Adjust to pH 4 with beta-alanine
G. Acidic Fixer Fluid 1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5
37.50 EHPD 7.5 37.50 ammonium nitrate 0.5 2.50 succinic acid 4
20.00 Na PAA 2000 3 15.00 DI Water 362.50 Total 515.00 Adjust to pH
4 with beta-alanine H. Acidic Fixer Fluid 1,5-pentanediol 8 40.00
2-pyrrolidinone 7.5 37.50 EHPD 7.5 37.50 ammonium nitrate 0.5 2.50
succinic acid 7 35.00 Na PAA 20,000 3 15.00 DI Water 347.50 Total
515.00 Adjust to pH 4 with beta-alanine I. Acidic Fixer Fluid
1,5-pentanediol 8 40.00 2-pyrrolidinone 7.5 37.50 EHPD 7.5 37.50
ammonium nitrate 0.5 2.50 succinic acid 4 20.00 Na PAA 20,000 3
15.00 DI Water 362.50 Total 515.00 Adjust to pH 4 with beta-alanine
Note: EHPD = 2-ethyl-2-(hydroxymethyl)-1,3-propanediol DI water =
de-ionized water Na PAA = sodium salt of polyacrylic acid
A wet rubbing test and a water drip test were performed on all
samples to see how much colorant was transferred. The wet rubbing
test was based on the TAPPI (Technical Association of the Pulp and
Paper Industry) 830PM-92 method (ink rub test of containerboard).
The water drip test comprised setting a printed sample at
45.degree. and dripping water over the ink. Visual observation is
sufficient to determine if colorant is transferred across the sheet
by the water.
In all cases, the overprinted areas, that is, areas overprinted
with fixer, showed better wet rub fastness and wet drip fastness
than areas that were only covered with magenta ink.
The pH of fixers C-E were not adjusted with alkali, and the pH of
these fixers ranged from 2 to 2.5.
Fixer A failed the water dip test, due to the presence of the
surfactants, but was better than no fixer at all. From this result,
it is clear that little or no surfactant should be used in the
fixer compositions of the present invention. Examples of
surfactants to be avoided, to the extent possible, include the
Tergitols, the Surfynols, and other surfactants with HLB values in
the range of 6 to 25.
Comparing the succinic acid-containing fixers above (B, F, G, H,
I), ranking of the pens used in increasing the water rub fastness
of the porous media is as follows (from most to least
effective):
However, even the least effective formulation still gave
significantly better waterfastness than samples without
overprinting.
The presence of succinic acid and/or higher molecular weight
(20,000) polymer of sodium polyacrylic acid (NaPAA) appears to help
water rub fastness. With regard to fixers C, D, and E, these were
not printed with the fixer fluid; rather, the fixer fluid was
simply poured over the printed medium and then rubbed. Very minimal
or no pigment transfer was observed for these three fixers,
compared to not pouring and then rubbing, which resulted in rubbing
off (80-90%) of the printed image.
INDUSTRIAL APPLICABILITY
The fixer fluid composition is expected to find use in ink jet
printing for increasing waterfastness of inks printed on media.
* * * * *